Voltammetric detection and analysis of the behavior of diethylstilbestrol oxidation products

Peroxidase‐mediated oxidation of diethylstibestrol (DES), a synthetic estrogen, has been proposed as a pathway in DES‐induced carcinogenicity. However, the transient nature of the DES oxidation product, DES‐quinone (DES‐Q), requires a rapid method such as cyclic voltammetry to study its stability and reactivity. Thus, the irreversible tautomerization of DES‐Q into dienstrol form (Z, Z‐DIES) is described by a two step mechanism. Tautomerization kinetics are studied as a function of pH and temperature. A significant descrease of half‐life for DES‐Q is observed in the presence of the glutathione thiolate form. Furthermore, voltammetric investigations were performed in dimethylformamide to detect the semiquinone radical of DES‐Q, a suspected genotoxic product.